Dinitrophenyl hydrazones as age-resistant in compounded high polymer products



United States Patent 3,010,939 Patented Nov. 28, 1 961 ice The present invention relates to a new class of age resisters for resinous high polymers to provide protec tion against the deteriorating effects of heat, light, and weathering. More particularly this invention is concerned with the use of dinitrophenyl hydrazones as age resisters in compounded high polymer products.

The search for new, more effective age resisters for natural and synthetic rubbers, and synthetic resins which are produced in sheet, film, fiber and molded forms, is a never-ending one. Articles which are exposed to the deteriorating effects of weather tend to stiffen, discolor, surface crack, check or craze, and lose appreciable amounts of their physical strength in relatively short periods of time.

It is an object of this invention to provide high polymer compounds which are exceptionally resistant to deterioration by light and weather.

It is another object of this invention to provide a class of age resister materials that can be readily compounded into a wide variety of natural and synthetic high polymer materials and that will invest said polymers with outstanding properties of age and deterioration resistance.

A further object is to provide high polymer materials compounded with 2,4-dinitrophenyl hydrazones which are suitable for forming fibrous, sheet, film, molded, cast and other solid objects that are extremely resistant to deterioration by heat, light and weather. Light, particularly ultra violet light with a wavelength of 300-400 m is one of the most destructive forces in the electromagnetic spectrum. It tends to degrade polymeric materials by discoloration, surface cracking, embrittlement and physical weakening by loss of tensile strength. Heat, on the other hand, literally boils and vaporizes many compounding ingredients right out of the polymer. Weathering produces ozone cracks, and sun checks, and fosters bleeding and leaching of both physically and chemically bound deterioration retarders and other compounding ingredients. The net effect is to leave articles composed of, or containing, high polymer parts severely discolored, cracked, stiff and weak in relatively short periods of time.

I have discovered that nitrophenyl hydrazones are strikingly effective in protecting high polymer materials,

from the stiffening, cracking and staining effects of aging and weathering. Hydrazones are defined as condensation products containing the trivalent N=H.N:C= group, resulting from the action. of compounds containing N.NH (hydrazines) with compounds containing (aldehydes and ketones). More particularly, I find that 2,4-dinitrophenyl hydrazones are extremely eifective when compounded in high polymer stocks to inhibit the deteriorating effects of weathering such as surface degradation, stiffening and embrittlement. Most preferred of .my new deterioration retarders are 2,4-dinitrophenyl by- 2 drazones formed by combining 2,4-dinitrophenyl hydrazine in equimolar proportions with a compound containing a reactive carbonyl,

group. Included in the groups of compounds containing a reactive I Q0 7 group are the chemical families of the aldehydes and ketones, including the so-called sugar aldehydes (aldoses).

The hydrazones contemplated for use in this invention include those Within the general formula where R is hydrogen, an alkyl radical preferably con taining 1 to 15 carbon atoms, aryl, or aralkyl, and R is hydrogen, an alkyl radical preferably containing 1-15 carbon atoms, an alkene radical containing ethylenic unsaturation (such as vinyl, allyl, or methallyl), and up to 9 carbon atoms, an aryl radical containing from 1 to 3 structural rings of carbon atoms or the reaction product of an aldose sugar with either a mon'oisocyanate or a diisocyanate. It is also understood that any of the beforelisted structures for R and R with the exception of hydrogen itself, may have any reactive hydrogen replaced by another substituent group such as halogen, nitro, hy-

droxyl, carboxyl, or cyano and alkoxy or alkyl radicals containing from 1 to 4 carbon atoms. These materials are readily prepared by reacting 2,4-di-nitrophenyl hydra-,

zine with the proper carbonyl compound to give the desired phenyl hydrazone. In the formulaabove the element comes from the carbonyl moiety of the reactants and the portion 1 OaN- N-N= comes from the dinitrophenyl hydrazine.

When a sugar compound such as glucose is employed to prepare the dinitrophenyl hydrazone, it has been found advantageous to further react some of the available hydroxy groups with a material such as met-aphenylene diisocyanate or phenylisocyanate to improve solubility in the high polymer stock.

of the selected carbonyl compound in 20 m1. of 95% ethanol. Add the fresh 2,4-dinitrophenyl hydrazine solution and let the mixture stand at room temperature. The 2,4-dinitrophenyl hydrazone will usually crystallize in 5 to minutes. If there is no precipitate in a short while, allow the mixture to stand overnight. The precipitate is readily separated by filtration.

The amount of 2,4-dinitrophenyl hydrazone that must be added to a polymeric material to provide adequate deterioration resistance varies somewhat depending on the composition of the base polymer employed. Proper amounts for any given polymeric material can readily be found by using regular mixing and compounding techniques for the particular polymer and then running standard ASTM tests such as tensile, elongation, oxygen bomb and weatherometer aging on test samples. In gen eral, any amount of nitrophenyl hydrazone above 0.5 part per 100 parts of polymer will give some beneficial efliects for deterioration resistance. More than about 10 parts will often be found to give less and less benefits for the additional material added and above this amount, the hydrazones may be incompatible with the base polymer. From 0.5 to 7.0 parts of dinitrophenyl hydrazone based on 100 parts of polymer usually gives beneficial results with 2.0 to 5.0 parts being most preferred.

I have found that dinitrophenyl hydrazones papear to be unique in providing the desired deterioration resistance for high polymer materials. When compounds containing other substituent groups, such as bromo, chloro, and carboxyl, in place of the nitro groups in the hydrazine moiety, were employed, the favorable results of the practice of my invent-ion were not obtained.

Compounds illustrative of this new class of deterioration retarders include the 2,4-dinitrophenyl hydrazones of di-n-butyl ketone, phorone, acetophenone, benzophenone, 2-octanone, p,p'-dimethoxybenzophenone, palmitone, formaldehyde, acetaldehyde, aorolein, chloral, isopentaldehyde, heptaldchyde, citronellaldehyde, anisaldehyde, crotonaldehyde, tiglic aldehyde, benzaldehyde, meta-nitrobenzaldehyde, cinnamaldehyde, naphthaldehyde, anthraldehyde, glucose and galactose.

The dinitrophenyl hydrazone deterioration retarders of my invention are broadly compatible by standard mixing and milling techniques with a wide variety of high polymer materials including polyether and polyester urethanes, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyacrylates, polymethacrylates. The term high polymer is intended to cover homopolymers, copolymers, tel-polymers, interpolymers and the like. The polymers may be compounded with fillers and loading pigments, accelerators, vulcanizing agents, retarders, and the like and the nitrophenyl hydrazones of my invention are still compatible therewith 4 The following examples in which parts are by weight illustrate my invention:

EXAMPLE 1 A polyesterurethane polymer was prepared according to the teachings of United States Patent 2,871,218 by mixing 1447 grams (1.704 mols) of hydroxyl polytetramethylene adipate, molecular weight 849, hydroxyl number 130.4, and 109.6 grams (1.218 mols) of butanediol- 1,4 in a kettle and stirring with a spiral ribbon stirrer for 20 minutes at a pressure of 5 to 6 mm. at 105 C. Next 730 grams (2.92 mols) of diphenyl methane-p,-pdiisocyanate were added and stirred into the mix for one minute. The reaction mass was then poured into a lubricated container, sealed with a friction top, and placed in a 140 C. oven for 3.5 hours. A clear, snappy elastomer was obtained.

One portion of the polyesterurethane polymer was maintained as a control. Other portions were mill-mixed with varying amounts of several 2,4-dinitrophenyl hydrazones. Micro tensile, 300% modulus and elongation were measured at the time the samples were prepared and at one month intervals over a period of one year while the samples were subjected to continuous outdoor weatherings by exposing 25 mil micro dumbbells mounted at a 45 angle in a unshielded position facing south. A summary of the test results is given in Table 1A. The A columns list data on the samples as originally prepared; B columns list similar figures after the samples have weathered for one year. The column headed Percent retention following the tensile strength comparison indicates the percent of original tensile strength still retained by the sample after the test period. If at least 50 percent of the original tensile strength is retained after 1 year of outdoor weathering, the age resister is doing its job. Furthermore, the sample should not develop any visible cracks, or at the most, only small ones no larger than hairline in width and of no appreciable depth. Samples were examined visually for cracks and arbitrarily rated as follows:

n--no cracks vvs-very, very small cracks vsvery small cracks s-small cracks rn-medium cracks l-large cracks Some compounded elastomer samples were exposed to another severe test, one week exposure under dry conditions in an Atlas Twin Arc Weather-Ometer, type HVDLX. These test data are shown in Table 1B. As in the outdoor tests, if the sample retains 50% or more of its original tensile strength after one Week in the weatherometer, the age resister is doing a good job. When viewed by the naked eye, the samples should not have through arange of 0.1 to 10.0 parts or more. developed more than very slight surface cracks.

Table 1A Tensile strength, 300% modulus, Elongation, per- Conc., p.s.1. Percent p.s.i. cent Cracks 2,4 dinitrophenylhydrazone p retendeveltton oped A B A B A B r. 5st: 1228 i888 1283 1 5 575 5 Pentaldehyde 2.0 8:900 71400 83.2 1.700 11400 510 500 vs 5. 0 9,000 7, 400 82. a 1, 400 1, 400 550 000 n 0. 0 7, 000 2, 200 31. 4 2, s00 550 200 m 0. 5 s, 600 5, s00 57. 4 2, 200 2,000 500 500 s 2-octanone 1.0 0,000 0,400 71.2 2,400 2,000 575 510 s l 2.0 10,000 7,200 72.0 1,900 1,800 575 550 vs 5. 0 9, 000 7, 100 78.8 1, 900 1, 400 500 000 11 9'8 2'388 288 33'? i288 1' m 700 075 s Cmmnaldehyde 2.0 6,600 51000 75.7 2,000 11100 625 675 n 5. 0 7, 000 s00 08. 7 2, 000 1, 100 050 675 n 0. 5 0, 700 2, 400 35. s 1, 600 1,000 650 000 m Benzophenone 1.0 7,100 3,200 45.1 1,100 800 700 625 s 5. 0 7, 100 3,600 50. 7 1, 200 800 025 700 s Table 1B Tensile strength, 300% modulus, Elongation, per- Oonc., p.s.i. Percent p.s.l. cent Cracks 2,4 dlnltropheuylhydrazone ph. retendeveltlon p A B A B A B 2-2 2222 92-2 2222 222 222 m I a 1 v s Bmmhmme 2.0 6,800 5,800 85.4 1,100 1,200 700 800 vs 5.0 4,800 4,000 83.4 800 1,100 700 725 vvs 2-2 2222 2222 22-2 222 "22-- 222 m 2 1, 1, 0 vvs Benzaldehyde 2.0 8,600 7,500 87.3 1,300 1,800 625 625 vvs G1 24am h 1 h at 5.0 8,400 6,000 71.5 1,600 1,900 575 625 n P Y 5.0 7,800 6,000 77.0 1,000 1 400 525 600 vvs gggg f lsmyanate eacmn 10.0 7,200 5,600 77.8 1,200 1:200 525 700 vvs Crotonaldehyde 1.0 0,600 5,600 58.3 2,000 1,800 400 510 s Oitronellaldehyde 1.8 9,600 6,800 71.8 1,700 1,800 535 600 vs EXAMPLE 2 pre ared by dryin 100 arts Teracol 30 at 100 C. and

P g P 2 mm. Hg for one hour, then adding 9 parts pPDI and A polyether urethane casting composition was prepared by reacting 0.017 mol of Teracol 30 (a hydroxypolytetramethylene oxide), 0.025 mol p-phenylene diisocyanate (pPDI) and 0.004 mol of trimethylolpropane in a glass flask equipped with stirrer, thermometer, vacuum connection and heating collar. The Teracol 30 was dried under vacuum at 100 C. Parapheny-lene diisocyanate was added at 100 C. and the mixture was stirred 15 minutes. Finally, the glycol was added, stirred for 8 minutes under vacuum, and the polymer mix was cast into closed curing molds and held for 16 hours at 130 C. The Teracol had a molecular weight of 2950, a hydroxyl number of 37.7, and an acid number of 0.1.

When a 2,4-dinitropheny1 hydrazone was to be incorporated, it was added before the glycol addition and in all cases mixed readily into the polymer mass. A control and test samples were placed in the weatherometer for one Week. Test data are listed in Table 2A. Column A lists results on freshly prepared samples; column B lists the comparable data after one week in the weatherometer.

Another control and test samples were cut in the form of micro dumbbells and hung in a 130 C. oven. At intervals, samples were removed and tested. Data are presented in Table 23. Under these severe conditions the age resistor is doing a remarkable job if it enables the sample to retain any strength after 24 hours. observed that unprotected control samples melt completely away in less than 24 hours.

degassing. Next 1 part 1,4-but-anediol, 0.35 part of potassium acetate, and 2 parts of 2octanone-2,4-dinitrophenylhydrazone were added and the mixture was again degassed. The polymer mass was then poured into micro tensile sheet molds and cured. for 16 hours at C.

Control and test samples were exposed in the weatherometer for one Week. The Teracol 30 had a molecular weight of 3000 and a hydroxyl number of 37.5.

a polyvinylchloride resinbymill mixing 30 parts of polyvinylchloride and 15 parts of a plasticizer, di-octyl phthalate, and then adding the desired amount of ageresister based on the parts of resin present. The resin and plasticizer formed a homogeneous mass on the mill Table 2A 0 c Tensile strength, P t 300% moidulus, Elongatlotmper- O k 011 .SJ. 810611 C811 T80 8 2,4 dinltrophenylhydrazone ph. p retenps develtion oped A B 1 A B A B 0.0 3,700 0.0 400 700 2.0 3,000 1,000 33.3 200 610 690 s 2.0 3,600 2, 400 66.7 400 200 700 625 vs 2-octanone 1.7 2,600 2,000 76.9 200 600 675 s 1 Melted away in 1 day.

Table 2B and the various 2,4-dinitroph'enylhydrazones all -mi1led into the batches very readily. 24mm h 1 C H 3 611 15: Per; 00 Etlon- 65 Table 4A lists the various test data obtained in the op en 0110. ours s reng cen mo 11- 2 ion hydrazone Y ph' maven mm lus Atlas weatherometer. Table 4B shows s1m1lar results non, cent obta1ned w1th samples exposed to outdoor weathering conditions for one year. Conn-01---- 0.0 0 3,700 -400 400 di ti c i u 2-octauone 2.0 0 6, 400 800 800 6 A g i Chara tar Snc of nprotected plasu 2'0 72 2,200 500 500 cized v1nyl resms 1s that they tend to darken, spot, and 168 discolor very quickly. The control sample employed "here in weatherometer testing showed the appearance lMeltedilllghoms- EXAMPLE 3 'of small black spots in 66 hours and was completely I black in 176 hours. Y Another polyether urethane casting composition was v76 At 1.0 p.h.r. crotonaldehyde-Z,4-dinitrophenylhydrazone, the first spot did not appear for 198 hours. Benzophenone-2,4-dinitrophenylhydrazone at 1.0 p.h.r. gave complete protection against spotting for 220 hours. With 1.0 p.h.r. chloral-2,4-dinitrophenylhydrazone after 198 8 EXAMPLE Several phenylhydrazones were prepared according to the procedure of Shriner and Fuson except that the nitro groups in 2,4dinitrophenylhydrazines were first replaced hours some p l of the Sample Was Observed- 5 by alternate substituent radicals or shifted to other posi- When the 2,4-dmltrophenylhydrazones of Q tions on the ring or removed entirely. These phenylhybeflzaldehyde al'ld P- y P y f y F were slmllal'ly drazones were compounded in the regular manner with compounded Yvlth P Y PY test ples the polyesterurethane polymer of Example 1. Results Showed Q Y mile darkening 5130111112 after 110 are summarized in Table 6A. Nitrobenzene and dinitroexposure 1n the weatherometer. 10 benzene were also included for comparison of the phenyl Table 4A Tensile strength, 300% modulus, Elongation, Gone. p.s.i. Percent p.s.i. percent Time, 2,4-dinitropheny1hydrazone ph. retention hours A B A B A B Control 0.0 3,500 0.0 300 198 Crotonaldehyde 1.0 2, 900 1,000 34.5 2, 900 300 220 Benzophenone 1.0 3,200 3,000 93.8 3,200 300 125 220 1.0 3,800 2, 000 70.4 3,000 325 125 198 Ohloral 3.0 3,200 4,200 131.0 2, 000 335 50 308 5.0 3,300 5,400 163.8 3,000 325 15 308 1 Too brittle to test.

Table 4B OUTDOOR EXPOSURE (12 MONTHS) ring with the 2,4-dinitrophenylhydrazone structure.

Tensile 300% modu Elongation, These results are shown in Table 6B. Initial data and 2, ostrength, 1115, p percent data taken after 1 week in the weatherometer are listed phenyl- Cone. p.s.1. cent T M 6A 6B hydrazone p11. retenm a and A B 0011 A B A B These data show that (1) the phenylhydrazone structure gives results superior to the phenyl structure, (2) that nitro substituent groups give better results than other 3,5 1,80 51.0 300 2 Ch1ora1 9.3 3,888 2,708 71.0 3,600 2 2 $98 subst1tuent rad1cals and (3) that better results are ob- 3 3,3 3,30 1000 3.100 3.300 325 300 40 tained when the nitro groups are in the 2 and 4 position on the phenyl ring in the phenylhydrazone structure.

Table 6A Tensile strength, 300% modulus, Elongation, per- Conc., p.s.i. Percent p.s.1. cent Cracks Phenylhydrazone ph. retendeveltion oped A B A B A B Croton aldehyde-p-nltrophenyl hy- 0.5 9,000 1,000 T 22.2 2, 000 1,400 600 400 1 drazone. 1.0 8,200 4,000 48.7 1,600 1,700 600 500 1 0.5 8,000 1,300 10.2 1,200 575 225 1 Benzaldebyde-2,4-dicl1lorophenyl- 1.0 8,400 1,800 21.4 1, 200 1,400 600 375 1 hydrazone. 2.0 8,500 2,800 32.9 1,400 1,500 575 450 1 5.0 9,200 3,700 40.3 1,400 1,700 600 m 0.5 0,300 1,700 18.3 2,400 1,700 550 300 1 Benzaldehyde-2,fi-diohlorophenyl- 1.0 9,100 2, 200 24.2 2,700 1,800 550 375 1 hydrazone. 2.0 9,100 2,300 25.2 2,700 1,700 550 400 1 5.0 9,500 3,800 40.1 2,200 1,800 600 500 m 0.5 10,400 1,600 15.4 2,000 1,500 500 225 1 Benzaldehyde-p-carboxyphenylhy- 1.0 9,000 1,500 16.7 2, 400 1,500 575 300 l drazone. 2.0 9, 900 2, 200 245 2,800 1,500 600 425 1 5.0 9,200 3,400 36.9 2,300 500 000 525 n 0. 0 7, 200 2, 600 36. 1 2, 400 3, 600 500 400 Benzophenonephenylhydrazone.. 0. 1 7, 000 2, 000 26. 4 2, 000 3, 100 525 400 1. 0 8, 000 2, 500 31. 3 2, 400 2, 600 425 525 Table 6B Tensile strength, 300% modulus, Elongation, per- Conc., Percent p.s.i. cent Cracks Benzene ph. reten develtion oped A B A B A B Nmo 2.0 8,700 1,600 18.4 2,000 575 200 1 5.0 8,000 2,000 25.0 1,900 1,700 575 325 1 Dinitro 2.0 8,000 4,200 52.4 1,800 1,800 600 500 1 It is seen that the 2,4-dinitrophenyl hydrazones com prise a class of extremely valuable age resistors for rubbery and resinous high polymers. These materials are highly compatible With the various types of polymers. They can be mill-mixed with millable polymers or mixed by mutual solvent techniques. They protect the physical properties of the polymers under extreme weathering conditions for long periods of time.

I claim:

T he combination comprising a mixture of 100 parts of a polymer selected from the group consisting of polyure thanes, polyethylene, polypropylene, polyvinylchloride, polyvinylidene chloride and polyacrylates With from 0.5 to 10.0 parts of a 2,4-dinitrophenyl hydrazone of the formula wherein R is selected from the group consisting of hydrogen, alkyl radicals containing 1 to 15 carbon atoms, phenyl, phenylmethoxy, and benzyl and R is selected from the group consisting of hydrogen, alkyl radicals Referencesfiited in the file of this patent UNITED STATES PATENTS 2,018,645 Williams et al. Oct. 22, 1935 2,044,800 Major et a1. June 23, 1936 2,067,299 Williams et a1. Ian. 12, 1937 2,165,525 Youker July 11, 1939 2,786,044 Warner et al. Mar. 19, 1957 FOREIGN PATENTS 552,448 Canada Jan. 28, 1958 

